Nitrogenous organic compounds and process of making same



. action mixture with aqueous caustic Patented June 19, 1945 UNITEDSTATES PATENT OFFlC mnoonivous oi'tGANrc COMPOUNDS AND raocess or MAKINGsum Arthur W. Bur-well and York James Allan Camellord, Niagara Falls, N.Y., assignors to Alox Corporation, New York, N. Y., a corporation of NewNo Drawing. Application November 13, i940, Serial Na. 365,540

2 Claims. (Cl. 260-583) process aspects and product aspects, andlikewise compositions containing the novel aminoderivatives.

It is to be understood that by the practice of the Burwell process upona starting material consisting essentially of a mixture'of saturatedhydrocarbons, such as a petroleum wax or a petroleum distillate (light,or heavy) there i produced an oxidation reaction mixture which iscomposed 01' two main classes of compounds, (1) a mixture of sc-called"saponiiiables" including saturated aliphatic carboxylic acids,saturated aliphatic hydroxy carboxylic acids, and esters and lactones01' said acids, and (2) a mixture of "unsaponiiiables includingsaturated aliphatic alcohols, saturated aliphatic ketones, saturatedaliphatic ketc-alcohols and some unoxidized (original) hydrocarbons. Thelatter mixture-the unsaponitiables"-may be separated, more or lesscompletely, from the saponiiiables by appropriate treatment of the wholeoxidation realkali at elevated temperature and separation of theresulting supernatant oily layer (composed of the unsaponiiiablecompounds) from the subnatant aqueous layer (composed of soaps oi thesaponiflable compounds). The present invention is concerned specificallywith the production oi amino-compounds in, and. at the expense or thealcohols and/or ketone of, the unsaponiflables portions 'of suchoxidation reaction masses derived from mixtures of saturated aliphatichydrocarbons of molecular weights corresponding to from 5 to, say, 36carbon atoms per molecule.

According to the present invention, to the "unsaponiilables portion ofthe oxidation reaction mixture there isadded, .in' excess, a reactiveamide, e. g., iormamide; the resulting mixture is heated gradually, atprogressively increasing temperature, until the water has been drivenoil and until the mixture has attained a temperature of approximately180 C., whereupon the mixture is maintained at about=the latter valuefor from 4 to hours. It is noted, here, that use of temperatures inexcess of 180 0., is undesirable because such temperatures tend toi'avor formation or cyanides in the mixture. When the reaction iscompleted, the reaction mixture is cooled and is washed with water. Theexcess or formamide may, if desired, be recovered from the wash water.The washed material is then treated at elevated temperature, e. g.,refluxed, with dilute mineral acid, e. g., dilute hydrochloricacid, forabout 2 hours, during which interval components of the material arehydrolyzed-as is shown by solution 'of a portion oi the total mass inthe aqueous layer, which separates, upon standing, from an oily 'ornon-aqueous layer, which latter demonstrably contains the maxidizedhydrocarbons and the alcohols of the original crude oxidation reactionmixture together i with a minor'amount of unreacted ketones. The aqueouslayer, rich in amine hydro-chlorides, is treated with cold causticalkali and then steam distilled to convert amine hydro-chlorides toamines. l

The resulting aminated product is a mixture of -many compounds, whichmixture defies separation into individual components and identificationof those individual components. That it contains amino-compounds isdemonstrable by the Kieldahl ammonia determination method. It isbelieved that the amines may be represented by the general formula 1OH-NHI 1v where R and R are allryl radicals the sum'of whose carbonatoms (per molecule of the amine) exceeds 5 and averages between 12 and24.

The above referred to "oily or non-aqueous layer" may be,-and Preferablyis, subjected to the 7 following further treatment for producingaminocyanamides from the halides.

compounds -i'rom the contained alcohols: the insoluble material, after.being washed with water arid dried, is treated with halogen acid, e. g.,an aqueous solution of hy'drobromic acid, or anhydrous HCl gas, until nofurther water is evolved, for the purpose of convertingalcohols to theircorresponding alkyl halides. Sodium cyanamide solution is then added tothe mixture and is reacted with the alkyl halides thereoLin the presenceoia suitable non-aqueous liquid medium,

as" methyl alcohol, in a still fitted with reflux condenser anddraw-oil. so a; to produce dialkyl Sodium halide is separated from themixture, and the latter is subiected to a treatment designed tohydrolyze the dialkyl cyanamides content thereoi, by treating Y of thepickled metal parts).

the mixture with aqueous mineral acid (e. g., 5111- phuric acid), forthe purpose of producing secondary dialkyl amines (of the type RaNH).

It is ,believed that where the alcoholic compounds contain two spacedhydroxyl groups along the chain, both hydroxyls may be replaced, to theproduction of saturated heterocyclic amino compounds.

Obviously, the above cyanamide process may be practiced upon the whole"saponifiables mass instead of upon the residue from theketone-converting process as described.

As was mentioned above, the product, in each case, is a mixture rich incompounds afflrmatively answering to established tests for organicamines and containing also many other different organicv compounds,which mixture-so far in 0111' researches-defies our attempts to separateit into its individual components- We have, nevertheless, found that therelative concentration of amines in the mixture may, in general, beincreased by steam distillation or the mixture in those cases where thevolatilities of the amines are sufficient to permit distillation Theproducts are solid to semi-liquid to liquid materials (depending on thesize of the molecule) from higher molecular weight mixtures (e. g.,v

compounds containing from 9 to, say, 36 carbon atoms per molecule) are,in general, im-

miscible with water; they are, however, completely miscible with mineralhydrocarbon liquids. value as means for preventing corrosion of metal(e. g., steel and iron) parts; moreover, they are adapted for use incorrosion-preventing compositions comprising other corrosion-preventingmeans.

preventing compositions described and claimed in U. S. Patent No.2,128,523 to Arthur W. Burwell; use of the aminatedproducts in suchcom-'- positions has been found effective for neutralizing any acidswhich may inadvertently be present in the same, wherebyto provide astrictly nonacid corrosion-preventing composition meeting the most rigidrequirements. Where such a corrosion-preventing composition is to beemployed on the inner surfaces of used airplane engine cylinders to bemaintained in standby condition for long or short periods, weincorporate into the composition a substantial proportion of the"aminated products for neutralizing the hydrobromic acid or iron bromidewhich mayipersist on said surfaces, or in the pores of the metal, in

the uppermegions of the cylinders, from the combustion'oi leaded gas"containing dibrom -x ethylene or the like.

These compositions-rich in amines find particular utility as eflectiveyet inexpensive corrosion' inhibitors in acidic-pickling baths, and' aspreparations for after-treating pickled metal 1 parts (to neutralize andfix residues of pickling acid left by indifferent or insufficientwashing The invention will be described with greater particularity withreference to the following examples:

The aminated products, per se, have Thus, it has been found that theyare. adapted to be incorporated in the corrosion- ExAmrLn 1 300 grams ofthe unsaponiflable portion of the oxidation mass from a 45 B. distillatewere mixed intimately with 80 grams or iormamide at 175 C., forapproximately 5 hours, using,

hydrolyzed mixture was washed 3 times with successive'small quantitiesof water until the lower water layer showed no qualitative test for.

chlorides by the silver nitrate method.

Determination of nitrogen by the Kjeldahl water-insoluble portion.

To 500 c. c. of-10% hydrochloric acid were added 5 grams of the abovewater-insoluble aminated product. A clean strip of steelwas introducedinto the acid-amine mixture at room temperature and at the end 01.5 daysshowed identical in composition and surface dimensions.

so Corrosion occurred immediately with the evoluacid immersion to anextreme degree.

The 5% hydrochloric acid which had i been used for the hydrolysis of theformyl derivative was taken, and the HCl concentration increased to 10%.A piece of steel identical with those used inthe abovetests wasintroduced into this acid. At the end of 5 days there was absolutely noindication of corrosion or attack. A check corrosion test was made usinguninhibited 10% HCl and using 10% HCl to which 1% of the water-insolubleaminated product had been added. At the end of 1 hour's immersion.at'room temperature a piece of .steel had lost .4'5% of its weight inthe 10% hydrochloric acid. In the acid inhibited withthe amine the lossof weight in a piece of steel or approximately identical surface areawas .003%.

4 EXAMPLE 2 v 300 grams of'the unsaponiflable portion of the oxidationmass from a B. distillate was treated with 250 grams of hydrobromie acid(48%) and '70 grams of concentrated sulphuric acid, The mixture wasrefluxed gently for 6 hours and thenthe mass was washed until the.

Collective volume 1, Gilman, page 197), together with 600 c.,c. of 95%ethyl alcohol, denatured.

at the end of which time about 500 c. c. of the alcohol-water weredistilled oil. The reaction mixture was then filtered, the filter washedwith a small amount of alcohol'and the filtrate ex- 7 tracted withbenzene. The benzene solution was then separated irom the lower layer,thebenzene distilled oiL-leaving a mixtureoi hydrocarbons,

method showed the presence of 57% N2 in the I tion of hydrogen and atthe end of 24 hours the immersed portion had shown the efifects of theThis mixture was refluxed for a period of 3 hoursv No inhibitor .Q

aavaeeo to prevent bumping, for a period of 6 hours. At the end of thistime the mass was cooled to room temperature, and 550 c. c. of 30%caustic soda solution were added down the side of the vesseldetermination on the amine mass showed a ni-.

trogen content of 42% N2. I

The corrosion-inhibiting property of the aminated products of Examples 1and 2 is numerically illustrated in the following table:

Table Solution 5% H 80 5 nminated product of Example 1 .5 same i 1.,same

While the animated products were desirably ef-.

tectivein preventing solution of the metal, it has been demonstratedthat they do not prevent solution of scale or oxide film on the surfaceof the metal. They are effective througha wide range of concentration,even down to as little as 0.1%. Relative to the above tests, it is herenoted 1. Process of preparing a mixture of waterlnsoluble butoil-soluble saturated aliphatic amines i'rom the ketones contained in anunsaponifiable mixture of unoxidized hydrocarbons, alcohols, and aplurality of different 'water-insoluble saturated aliphatic ketones ofthe gen r 'eral formula wherein R and R are alkyl radicals the sum ofwhose carbon atoms averages between 12 and 24;

which comprises treating said of hydrocarbons, alcohols and ketones withiormamide in excess, at a temperature between 100 C. and

180 0., for several hours, removing excess l'ormamide from the resultingreaction mixture by washing the latter with water, hydrolyzingcomponents of the washed material by treating the latter with an aqueoussolution of a mineral acid at elevated temperature and thereaiterallowing the reaction mixture to separate into a nonaqueous layercontaining the hydrocarbons and the alcohols of the original startingmaterial and an aqueous acidic layer containing hydrolyzed components ofthe reaction mixture, separating the aqueous layer from the non-aqueouslayer, and treating the aqueous layer with dilute caustic alkali in thecold whereby the hydrolyzed that a. very substantial inhibiting effectis had by associating with the acid pickling bath about 1% by weight ofthe water-insoluble animated-products from the unsaponifiablesf fromoxidized scale wax (where the hydrocarbon chains contain as many as asor 28 carbon atoms per molecule). .Even though these very high molecularvweight,aminate'ed products are quite insoluble in water, theynevertheless show considerable corrosioninhibiting eilect in a 5% H2504pickling bath. v

components are converted to a mixture of waterinsoluble but oilsolubleamines.

29 As a new product, a water-insoluble but petroleum-soluble compositionconsisting essentialhr of amino derivatives of a mixture of diflerentsaturated aliphatic ketones averaging between 12 and 24 carbon atoms permolecule, said composition having corrosion-inhibiting properties andbeing obtained by the process defined in claim 1.

ARTHUR. W. nuawmn JAB/ES ALLAN CAMELFORD.

